CN105016618B - A kind of near-infrared luminous bismuth doping multicomponent glass and preparation method thereof - Google Patents
A kind of near-infrared luminous bismuth doping multicomponent glass and preparation method thereof Download PDFInfo
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- CN105016618B CN105016618B CN201510424527.1A CN201510424527A CN105016618B CN 105016618 B CN105016618 B CN 105016618B CN 201510424527 A CN201510424527 A CN 201510424527A CN 105016618 B CN105016618 B CN 105016618B
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- glass
- bismuth
- infrared luminous
- multicomponent
- doping
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 46
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000011521 glass Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000137 annealing Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 239000000156 glass melt Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005352 clarification Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000835 fiber Substances 0.000 abstract description 10
- 239000013307 optical fiber Substances 0.000 abstract description 8
- 239000000377 silicon dioxide Substances 0.000 abstract description 7
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 abstract description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 abstract description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- 238000004031 devitrification Methods 0.000 abstract 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 abstract 1
- 229910003443 lutetium oxide Inorganic materials 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention discloses a kind of near-infrared luminous bismuth doping multicomponent glass, including La2O3、Y2O3、Lu2O3、Ga2O3、In2O3、MgO、CaO、SrO、BaO、Bi2O3、GeO2；Adulterated in the near-infrared luminous bismuth of glass the invention also discloses above-mentioned glass the preparation method of multicomponent glass.Near-infrared luminous bismuth doping multicomponent glass of the invention, after softening temperature treatment, can keep broadband near-infrared luminous, and not crystallization, not devitrification, and this is that other bismuths doping multicomponent glass cannot be completed；Glass of the present invention 950~1600nm of luminous covering, light halfwidth>200nm, is wider than bismuth doping silica fibre, is expected to be applied in fields such as multicomponent optical fiber, wideband adjustable optical-fiber laser, ultra-short pulse lasers.
Description
Technical field
The present invention relates to the preparation field of glass, more particularly to a kind of near-infrared luminous bismuth doping multicomponent glass and its system
Preparation Method.
Background technology
Bismuth doped fiber is a class New Active glass optical fiber, near-infrared luminous with broadband, it is possible to achieve infrared 1-1.6
Micron waveband tunable laser is exported.The bismuth optical fiber of report is bismuth doping silica fibre at present, using metal organic-matter chemical gas
It is prepared by phase sedimentation (MOCVD).But this preparation method must be carried out at a high temperature of more than 2000 degree, and otherwise quartz cannot be soft
Change, it is impossible to optical fiber is obtained.Temperature so high will cause bismuth largely to volatilize, so obtained bismuth silica fibre, bismuth adulterates dense
Degree is low, and only 50ppm, gain is low, and fluorescence halfwidth is general in 100~150nm, it is difficult to break through 200nm.This is perhaps because bismuth
The reason that bismuth cluster ions luminophore cannot be formed when concentration is extremely low.Bismuth silica fibre gain is low, cannot be real using short fiber
Existing laser generation, is unfavorable for device miniaturization, intensive；Fluorescence halfwidth is narrow, and the wave-length coverage for causing laser tunable is narrow,
It is unfavorable for realizing the realization of ultra-short pulse laser simultaneously.How to realize that bismuth high-concentration dopant is the problem for perplexing bismuth optical fiber at present.
One of approach of solution is to prepare optical fiber using multicomponent glass.Multicomponent glass can be prepared in lower temperature, so can be by
Optical fiber preparation temperature lowers, and is prevented effectively from bismuth volatilization, realizes that bismuth is highly doped.But research finds, bismuth doping multicomponent glass exists
It is secondary by thermal softening, during drawing optic fibre, bismuth is near-infrared luminous would generally to disappear.It was found that it is secondary by thermal softening when, can stablize
The glass ingredient of bismuth valence state is crucial.But currently without the report of this respect.
The content of the invention
In order to overcome the disadvantages mentioned above and deficiency of prior art, it is an object of the invention to provide a kind of near-infrared luminous bismuth
Doping multicomponent glass, it is secondary by thermal softening when, glass can stablize the near-infrared luminous center of bismuth.
Another object of the present invention is to provide the preparation method that above-mentioned near-infrared luminous bismuth adulterates multicomponent glass.
The purpose of the present invention is achieved through the following technical solutions：
A kind of near-infrared luminous bismuth doping multicomponent glass, the molar percentage of each oxide component is：
A kind of preparation method of near-infrared luminous bismuth doping multicomponent glass, comprises the following steps：
(1) raw material is weighed by the molar percentage of each oxide component：
(2) after the raw materials of compound that step (1) is weighed is ground, crucible is placed in, under air pre-burning；
(3) by after step (2) pre-burning sample take out, after being ground, be placed in crucible, under air melt, stirring,
Change, clarify, obtain glass melt；Glass melting temperature is 1000~1350 DEG C, and melting time is 0.5~2 hour；
(4) glass melt that step (3) is obtained is poured on mould, after natural cooling, solidification, moves to and move back in annealing furnace
Fire, eliminates residual stress, and near-infrared luminous bismuth doping multicomponent glass is obtained.
Step (1) described pre-burning, specially：
Calcined temperature is 400~700 DEG C, and the time is 1~5 hour.
Step (4) described annealing, specially：
In 600~700 DEG C of annealing, the time is 1~5 hour.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) near-infrared luminous bismuth doping multicomponent glass of the invention can be made between 1000~1300 DEG C of lower temperature
It is standby, bismuth volatilization can be prevented effectively from, it is capable of achieving the doping of high concentration bismuth, doping concentration>5mol%, i.e., more than 50000ppm, be far above
Bismuth doping concentration~50ppm in quartz glass, doping concentration improves more than 1000 times.
(2) near-infrared luminous bismuth doping multicomponent glass of the invention 950~1600nm of luminous covering, light halfwidth>
200nm, is wider than bismuth doping silica fibre.
(3) near-infrared luminous bismuth doping multicomponent glass of the invention light it is excellent, in 900~980 DEG C of softening temperature again
Secondary heating, it is luminous to keep, illustrate luminous thermally-stabilised good, this is not available for current other bismuths doping multicomponent glass.
Brief description of the drawings
Fig. 1 is the luminous of the near-infrared luminous bismuth doping multicomponent glass of different lanthanum contents prepared by embodiments of the invention
Figure.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment
The preparation process of the near-infrared luminous bismuth doping multicomponent glass of the present embodiment is as follows：
(1) with lanthana, yittrium oxide, luteium oxide, gallium oxide, indium oxide, magnesia, calcium carbonate, strontium carbonate, barium carbonate,
Bismuth oxide, germanium oxide are raw material, and raw material is weighed by mole composition described in table 1, and it is 100g to control gross weight.
(2) after the raw materials of compound that step (1) is weighed is ground, crucible is placed in, is joined according to the technique described in table 1
Number carries out pre-burning；
(3) sample after step (2) pre-burning is taken out, after being ground, crucible is placed in, according to the technique described in table 1
Parameter is founded under air, is stirred in melting process, be homogenized, clarified, and is removed bubble removing, is improved glass uniformity；
(4) by glass melt rapid dumps in step (3) on mould, after natural cooling, solidification, annealing furnace is moved to, is pressed
Annealed according to the technological parameter described in table 1, eliminated residual stress, glass sample is obtained.
The composition of the glass sample manufactured in the present embodiment of table 1, technological parameter and luminous situation
Glass manufactured in the present embodiment is transparent and bubble-free, and bismuth doping concentration is above 5mol%, i.e. 50000ppm, far
Higher than the 50ppm of bismuth doping silica fibre.Fig. 1 is the illuminated diagram of different lanthanum content glass manufactured in the present embodiment, as seen from the figure,
Glass, with luminous, during lanthanum content 0%, corresponds to component 11.00Ga in 950-1600nm2O3-17.00BaO-6.00Bi2O3-
66.00GeO2, positioned at 1234nm, light luminous peak position halfwidth 242nm；During lanthanum content 2%, correspondence component 2.00La2O3-
11.00Ga2O3-17.00BaO-6.00Bi2O3-64.00GeO2, positioned at 1224nm, light luminous peak position halfwidth 238nm；Lanthanum contains
When measuring 6%, correspondence component 6.00La2O3-11.00Ga2O3-17.00BaO-6.00Bi2O3-60.00GeO2, luminous peak position is located at
1206nm, light halfwidth 234nm.Increase with lanthanum content, glow peak blue shift, halfwidth narrows, but is wider than 200nm.This reality
The luminous of glass for applying example preparation is wider than bismuth doping silica fibre.
Glass manufactured in the present embodiment is heat-treated at 900~980 DEG C of softening temperature, and glass keeps transparent, without crystallization, tool
There is 950-1600nm to light.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by the embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (4)
1. a kind of near-infrared luminous bismuth doping multicomponent glass, it is characterised in that the molar percentage of each oxide component is：
2. a kind of near-infrared luminous bismuth adulterates the preparation method of multicomponent glass, it is characterised in that comprise the following steps：
(1) raw material is weighed by the molar percentage of each oxide component：
(2) after the raw materials of compound that step (1) is weighed is ground, crucible is placed in, under air pre-burning；
(3) sample after step (2) pre-burning is taken out, after being ground, is placed in crucible, melt under air, stir, being homogenized,
Clarification, obtains glass melt；Glass melting temperature is 1000~1350 DEG C, and melting time is 0.5~2 hour；
(4) glass melt that step (3) is obtained is poured on mould, after natural cooling, solidification, moves to annealing in annealing furnace,
Residual stress is eliminated, near-infrared luminous bismuth doping multicomponent glass is obtained.
3. near-infrared luminous bismuth according to claim 2 adulterates the preparation method of multicomponent glass, it is characterised in that step
(2) pre-burning, specially：
Calcined temperature is 400~700 DEG C, and the time is 1~5 hour.
4. near-infrared luminous bismuth according to claim 2 adulterates the preparation method of multicomponent glass, it is characterised in that step
(4) annealing, specially：
In 600~700 DEG C of annealing, the time is 1~5 hour.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510424527.1A CN105016618B (en) | 2015-07-17 | 2015-07-17 | A kind of near-infrared luminous bismuth doping multicomponent glass and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510424527.1A CN105016618B (en) | 2015-07-17 | 2015-07-17 | A kind of near-infrared luminous bismuth doping multicomponent glass and preparation method thereof |
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| CN105016618B true CN105016618B (en) | 2017-06-06 |
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| CN107698165A (en) * | 2017-07-31 | 2018-02-16 | 同济大学 | A kind of devitrified glass containing bismuth germanium oxide crystalline phase and preparation method thereof |
| CN111217524B (en) * | 2018-11-27 | 2022-05-06 | 宜城市泳瑞玻璃科技有限公司 | High-refractive-index mid-infrared optical glass and preparation method thereof |
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Effective date of registration: 20231012 Address after: Room 602-5, Building 9, No. 68 Dakang Road, Qingshanhu Street, Lin'an District, Hangzhou City, Zhejiang Province, 311300 Patentee after: Hangzhou Qilian Fiber Optic Technology Co.,Ltd. Address before: 510640 No. five, 381 mountain road, Guangzhou, Guangdong, Tianhe District Patentee before: SOUTH CHINA University OF TECHNOLOGY |
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